EP2740781A1 - Schäumzusammensetzung mit benetzbarkeitsmodifizierenden und korrosionshemmenden Eigenschaften für hohe Temperaturen und ultrahohen Salzgehalt - Google Patents

Schäumzusammensetzung mit benetzbarkeitsmodifizierenden und korrosionshemmenden Eigenschaften für hohe Temperaturen und ultrahohen Salzgehalt Download PDF

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EP2740781A1
EP2740781A1 EP20130187430 EP13187430A EP2740781A1 EP 2740781 A1 EP2740781 A1 EP 2740781A1 EP 20130187430 EP20130187430 EP 20130187430 EP 13187430 A EP13187430 A EP 13187430A EP 2740781 A1 EP2740781 A1 EP 2740781A1
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sodium
sulfonate
hydroxysultaine
wettability
alkyl
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EP2740781B1 (de
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Raúl HERNÁNDEZ ALTAMIRANO
Luis Silvestre Zamudio Rivera
Violeta Yasmín Mena Cervantes
Erick Emanuel Luna Rojero
Enrique Serrano Saldaña
José Manuel Martínez Magadán
Raúl Oviedo Roa
David Aarón Nieto Alvarez
Eduardo BUENROSTRO GONZÁLEZ
Rodolfo Cisneros Devora
María del Pilar Arzola García
Mirna Pons Jiménez
América Elizabeth Mendoza Aguilar
Sung Jae Ko Kim
Jorge Francisco Ramírez Pérez
Tomás Eduardo Chávez Miyauchi
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Instituto Mexicano del Petroleo
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Instituto Mexicano del Petroleo
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
    • E21B41/02—Equipment or details not covered by groups E21B15/00 - E21B40/00 in situ inhibition of corrosion in boreholes or wells
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons

Definitions

  • the present invention is related with obtaining and using foaming compositions with wettability-modifying and corrosion inhibitory properties that control the channeling of fluids in naturally fractured carbonate reservoirs, favorably alter the rock wettability in crude oil enhanced recovery processes and control uniform corrosion problems occurring in production rigs under high temperature and ultra-high salinity conditions; by means of the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulfonates and sodium alkenyl sulfonates (1).
  • the foaming compositions with wettability-modifying and corrosion inhibitory properties are characterized for being tolerant to high concentrations of divalent ions such as calcium, magnesium, strontium and barium and for the fact that for its application in the reservoir, sea water and/or congenital water characteristic of the reservoir may be used as means of transportation.
  • NFCR naturally fractured carbonate reservoirs
  • chemical products used therein in order to increase the recovery factor must be able to control the channeling of fluids and to alter the rock wettability from oil-wettable to water-wettable.
  • chemical products to be used in enhanced recovery processes are required to be tolerant to high salinities and divalent ions concentrations and to control corrosion problems occurring in the production rigs
  • the main chemical families of surfactants that have been used to generate foams and that have application in enhanced recovery processes include: 1) Alkyl aryl sulfonates (Patent US 5,273,682 ; Viscosity control additives for foaming mixtures), 2) Alkoxy alkyl benzenesulfonates (Patent US 5,049,311 ; Alkoxylated alkyl substituted phenol sulfonates compounds and compositions, the preparation thereof and their use in various applications), 3) Alpha olefin sulfonates (Patent US 4,607,695 ; High sweep efficiency steam drive oil recovery method), 4) Alkyl amido Betaines (Patent US 7,104,327 ; Methods of fracturing high temperature subterranean zones and foamed fracturing fluids therefor), 5) Alkyl amido hydroxysultaines (Patent US 7,407,916 ; Foamed treatment fluids and associated methods) and 6) Alkyl
  • foaming agents' formulations with enhanced properties have been developed, including as the following:
  • US patent 4,703,797 (Sweep improvement in enhanced oil recovery) mentions a new enhanced method for sweeping during enhanced hydrocarbon recovery processes.
  • the method comprises the generation of foam by means of dispersion of the displacement fluid in an aqueous solution containing a formulation of surfactants.
  • Said surfactant formulation comprises a lignosulfate-based foaming agent and a foaming surfactant.
  • the foaming surfactants that are mentioned include the group comprising anionic, non-ionic and amphoteric surfactants.
  • US patent 5,295,540 (Foam mixture for steam and carbon dioxide drive oil recovery method) mentions a method based on foams to enhance hydrocarbon production in subterranean formations consisting of: 1) Injecting steam and produced fluids into the formation and 2) Injecting a mixture of steam, a non-condensable gas and an aqueous mixture of surfactant and polysaccharides.
  • the surfactants mentioned that may be used include linear toluene sulfonates, alkyl aryl sulfonates, dialkyl aryl sulfonates, alpha olefin sulfonates and alpha olefin sulfonate dimers.
  • US patent 5 542,474 (Foam mixture for carbon dioxide drive oil recovery method) refers to a foam-based method to enhance performance during the supply of steam or carbon dioxide in subterranean formations containing crude oil and that comprise at least a producing well and an injection well.
  • the sweeping efficiency in the oil-recovery process by means of steam supply is enhanced by: 1) injecting steam until it starts to appear in the producing well and 2) Subsequently adding a mixture of steam, non-condensable gas and an aqueous solution of a surfactant-polypeptide.
  • the aqueous surfactant-polypeptide solution forms stable foam with the formation oil at reservoir conditions.
  • Surfactants used as base for the foaming agent include sodium and ammonium salts of sulfated alcohol ethoxylates, linear alcohol ethoxylates and linear toluene sulfonates.
  • the article " Improving the foam performance for mobility control and improved sweep efficiency in gas flooding" mentions that the apparent stability and viscosity of a foam generated by alpha olefin sulfonates in brine having concentrations of 30,000 and 120,000 ppm of total solids dissolved is substantially enhanced when formulated with partially hydrolyzed polyacrylamide-based polymers or xanthan gum-type biopolymers. Furthermore, the article mentions that the stability of foams generated by twelve-carbon alpha olefin sulfonates is substantially increased when formulated with amine oxide-type surfactants.
  • US patent 5,911,981 (Surfactant blends for generating a stable wet foam) mentions a mixture of surfactants that generates stable spherical foams.
  • the mixture of surfactants contains a non-ionic surfactant or an amphoteric surfactant as the primary foaming agent, and sufficient amounts of an acyl lactylate to increase the volume of the foam and to provide an excess of spherically-shaped foam for time periods of approximately forty minutes.
  • amphoteric surfactants that are mentioned include betaines, sultaines and aminosultaines and the use of cocodimethylpropylsultaine, stearyldimethylpropylsultaine, lauryl-bis (2 hydroxyethyl)propylsultaine and cocoamidopropyl hydroxysultaine is specifically mentioned.
  • the US patent 7,104,327 provides methods to fracture high-temperature subterranean zones and foamed aqueous and viscous fracturing fluids for this purpose.
  • the fracturing fluid of said invention comprises water, a 2-acrylamide-2-methylpropane sulfonic acid terpolymer, acrylamide and acrylic acid or salts thereof, a gas, a foaming agent and a viscosity breaker to control and reduce the viscosity of the fracturing fluid.
  • the foaming agent in said invention is selected from the group comprising C 8 -C 22 alkyl amido betaine, alpha olefin sulfonate, taloil trimethyl ammonium chloride, C 8 -C 22 alkyl ethoxilate sulfate and trimethyl coco ammonium chloride and special mention is made of cocoamidopropyl betaine as foaming agent.
  • alkyl amido propyl betaines with alkyl ether sodium sulfate and alkyl sodium sulfate-type anionic surfactants has been studied in literature ( Langmuir 2000, 16, 1000-1013 , Langmuir 2004, 20, 565-571 , Langmuir 2004, 20, 5445-5453 ) and it primarily suggests the ability of alkyl amido propyl betaines to stabilize and to improve the rheological properties (viscosity) of foams generated by said anionic surfactants and that have application in shampoos and hair conditioners.
  • the patent comprises methods to generate fluids for foamed treatments and to introduce them in subterranean formations. Furthermore, US patent 7,134,497 never mentions the use of sodium alkyl hydroxysulfonates and/or sodium alpha olefin sulfonates, or that the fluids for the foamed treatments have wettability modifying or corrosion inhibitory properties.
  • US patent 7,287 , 594 (Foamed Treatment Fluids and Associated Methods) refers to treatment methods for subterranean formations using foamed fluids comprising water, a gas and a foam, and mixtures of foam stabilizing surfactants comprising a range of alkali salts of alkyl ether sulfates, wherein the alkyl group in each of the alkyl ether sulfates is in the range of 4 carbon atoms to 10 carbon atoms, an alkyl amido propyl hydroxysultaine or an alkyl amido propyl betaine and an alkyl amido propyl dimethylamine oxide.
  • the patent does not mention the use of sodium alkyl hydroxy sulfonates and/or sodium alpha olefin sulfonates or that the foamed fluids have wettability-modifying or corrosion inhibitory properties.
  • US patent 7,373,977 Provides a hydrocarbon recovery composition and process, which comprise injecting an aqueous solution into a hydrocarbon-containing formation through one or more injection wells, displacing the solution within the formation and recovering the hydrocarbon through one or more producing wells.
  • the aqueous solution contains one or more amphoteric surfactants of the alkyl amido betaines-type (4) that form a viscoelastic surfactant gel that can reduce interfacial tension and increase injection fluid viscosity simultaneously in certain oils and brines.
  • Viscoelastic gels are tolerant to multivalent electrolytes and cations and are particularly useful within reservoirs with middle to high temperature, high salinities, high concentrations of divalent ions and low porosity.
  • the hydrocarbon-recovery compound contains one or more amphoteric surfactants selected for their ability to lower interfacial tension and to increase viscosity simultaneously, an aqueous medium, a secondary surfactant and, optionally, one or more polymers to provide residual viscosity.
  • the secondary surfactant can be selected from the anionic, cationic or non-ionic group and that the polymer that provides residual viscosity is selected from the group of polyacrylamide, partially hydrolyzed polyacrylamide, xanthan gum, hydroxyethyl cellulose or guar gum. Additionally, the patent application mentions that the combination of alkyl amido betaines with secondary surfactants of the linear type sodium dodecyl benzene sulfonate and sodium arylalkyl xylene sulfonate reduces interfacial tension and increases the viscosity of the system.
  • the patent includes methods to generate fluids for foaming treatments and to introduce them in subterranean formations. Additionally, US patent 7,407,916 never mentions the use of sodium alkyl hydroxysulfonates and/or sodium alpha olefin sulfonates, or that the fluids for foamed treatments have wettability modifying or corrosion inhibitory properties.
  • Mexican patent MX 297297 relates to an enhanced-stability foaming composition that controls gas channeling in naturally fractured carbonate reservoirs with high salinity and temperature conditions, by means of the synergistic effect resulting from the supramolecular interaction of sodium alpha olefin sulfonates with alkyl amido propyl betaines (5), wherein R and R1 are independent linear or branched alkyl chains with a length ranging from 1 to 30 carbon atoms.
  • the supramolecular complexes resulting from the interaction of sodium alpha olefin sulfonates with alkyl amido propyl betaines can be combined with anionic surfactants, preferably of the sodium 3-hydroxy-alkyl sulfonate-type, with cationic surfactants such as alkyl ammonium quaternary salts, preferably of the alkyl trimethyl ammonium chloride- or bromide-type, with divalent ions sequestrants, preferably itaconic acid-derived oligomers or copolymers and whose average molecular weight is within the range of 200 to 20,000 Daltons, with gels derived from copolymers selected from the group comprising polyacrylamides, partially hydrolized polyacrylamide, xanthan gum, Poly(itaconic acid), Poly(acrylic acid), Poly(itaconic acid-co-acrylic acid) poly(itaconates) and Poly(acrylates).
  • anionic surfactants preferably of the sodium 3-hydroxy-al
  • the patent application indicates that the enhanced-stability foaming compositions have applications in enhanced recovery and/or production assurance processes.
  • the patent application does not mention using alkyl amido propyl hydroxysultaine or alkyl hydroxysultaine-based compositions or that these have applications as wettability modifiers and corrosion inhibitors.
  • formulations with enhanced properties have been developed, such as the following:
  • US patent 6,828,281 (Surfactant Blends for Aqueous Solutions Useful for Improving Oil Recovery) mentions an aqueous fluid useful for liquid hydrocarbon recovery in subterranean reservoirs and where the aqueous fluid comprises an aqueous medium and a mixture of surfactants.
  • the mixture of surfactants contains at least a polyisobutylene-based synthetic surfactant and a secondary surfactant selected from the group comprising sulfonated surfactants, alcohols and ionic surfactants.
  • the surfactant mixture lowers interfacial tension between the hydrocarbon and the aqueous fluid.
  • supramolecular chemistry is the part of chemistry that takes care of the study of systems that involve molecules or ions aggregates that are bound through non-covalent interactions, such as electrostatic interactions, hydrogen bonds, ⁇ - ⁇ interactions, dispersion interactions and hydrophobic effects.
  • Supramolecular chemistry can be divided in two large areas: 1) Host-Guest Chemistry and 2) Self-assembly. The difference between these two large areas is a matter of size and form; where there is no significant difference in size and none of the species acts as host to the other, the non-covalent bonding between two or more species is termed self-assembly.
  • supramolecular interactions are much weaker than covalent interactions, which fall in the energetic range of 150 to 450 Kj/mol for simple bonds.
  • the non-covalent interactions energetic range goes from 2 kj/mol for dispersion interactions to up to 300 kj/mol for ion-ion interactions (Table 1), and the sum of several supramolecular interactions can produce highly stable supramolecular complexes.
  • Table 1 Supramolecular Interactions Strength Interaction Strength (Kj/mol) Ion-ion 200-300 Ion-dipole 50-200 Dipole-dipole 5-50 Hydrogen bond 4-120 Cation- ⁇ 5-80 ⁇ - ⁇ 0-50 Van der Waals ⁇ 5 Hydrophobic Related with the solvent-solvent interaction energy
  • Computational chemistry is a tool that is widely used throughout the world to predict the stability and structure of chemical systems with enhanced potential properties and has found application at industrial level in the development of quantitative structure-activity relationship studies.
  • Computational calculation methods that have been used for this purpose include molecular mechanics methods, quantum methods, which comprise semi-empiric and ab-initio methods, as well as the density functional theory methods.
  • the present invention relates to the synergistic effect resulting from the supramolecular interaction of alkyl amido propyl hydroxysultaines or alkyl amino hydroxysultaines with sodium alkyl hydroxysulfonates and sodium alkenyl sulfonates and its application in the development of foaming compositions with enhanced stability that control the channeling of fluids in naturally fractured carbonate reservoirs with ultra-high salinity and high temperature conditions, alter the wettability of the rock in a favorable way in enhanced crude oil recovery processes and control uniform corrosion problems that occur in production rigs.
  • the developed supramolecular complexes widely surpass commercial surfactants in terms of performance as foaming and wettability-modifying agents.
  • the supramolecular complexes based on sodium alkenyl sulfonates, alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines are characterized for being tolerant to brines with high concentrations of divalent ions such as calcium, magnesium, strontium and barium and for the fact that for its application to the reservoir, sea water and/or congenital water characteristic of the reservoir may be used as means of transportation.
  • the selection of the present methodology is based on the fact that the key point to solve the series of problems associated with the development of foaming agents with wettability-modifying and corrosion inhibitory properties that are tolerant to high salinity and divalent ions concentrations and able to endure high-temperature and pressure conditions is the understanding at molecular level of: 1) How to control the ionic exchange reaction between the foaming agent and the divalent ions present in the injection water and/or formation water; 2) How to generate dipole-dipole pairs between the agent with wettability-modifying properties and the polar compounds present in hydrocarbon so that these are able to alter the wettability of carbonate rocks from oil-wettable to water-wettable and 3) How to generate stable films, resulting from the interaction between the corrosion inhibitor and the corroded surfaces that are present in production rigs typical in the oil industry.
  • the first thing to establish in molecular design is how to control the ionic exchange reaction between the foaming agent and the divalent ions present in the injection water and/or formation water, and the first premise to consider is based on the fact that in order for the foaming phenomenon to take place, it is necessary that the foaming agent contains at least one atom of sodium or potassium and that this monovalent atom is substituted in traditional foaming agents by divalent ions, since the process is thermodynamically and kinetically favored as the temperature present in the system increases (Mexican patent MX 297297 , Composi letters Espumante para Alta Temperatura y Salinidad), and thus it would be necessary to find a way to encapsulate the sodium or potassium atoms by means of supramolecular chemistry.
  • Table 3 results analysis shows that the 2.520, 2.407, 3.672, 2.247, 2.244 and 2.270 ⁇ distances for interactions O1 ⁇ Na1 , O2 ⁇ Na1 , O2 ⁇ Na2 , O2 ⁇ Na2 , O11 ⁇ Na2 and O12 ⁇ Na1 are smaller than the sum of the Van der Waals Radius for the oxygen (Van der Waals Radius of 1.52 ⁇ ) and sodium atoms (Van der Waals Radius of 2.27 A) and are typical of structures containing Na-O coordination bonds and sulfonate groups ( Crystal Growth & Design 2006, 6[2], 514-518 ).
  • supramolecular complex 4 which could act as gas receptor and generate inclusion complexes that would behave as foaming agents in aqueous media.
  • this complex 4 shows that the sodium atoms have been encapsulated and therefore the new foaming agents must be tolerant to brines containing large quantities of divalent ions and to high temperatures.
  • Table 5 results shows that the formation of supramolecular complex 8 from the 1:1:2 molecular interaction of compounds 5, 6 and 7 would be strongly favored from the thermodynamic point of view. Additionally, the -264.160 kJ/mol interaction energy indicates that ion-ion-type supramolecular interactions and/or a combination of ion-dipole interactions and hydrogen bonds would be present. Table 4. Mulliken atomic charges of compounds 1, 2, 3 and supramolecular complex 4.
  • Table 6 results analysis shows that the 2.519, 2.407, 3.681, 2.247, 2.243 and 2.273 ⁇ distances for interactions O1 ⁇ Na1, O2 ⁇ Na1 , O2 ⁇ Na2 , O3 ⁇ Na2 , O11 ⁇ Na2 and O12 ⁇ Na1 are smaller than the Van der Waals Radii sum for the oxygen (Van der Waals Radius of 1.52 A) and sodium (Van der Waals Radius of 2.27 A) atoms and are typical of structures containing Na-O coordination bonds and sulfonate groups ( Crystal Growth & Design 2006, 6[2], 514-518 ).
  • supramolecular complex 8 shows the presence of a nanocavity and that the sodium atoms have been encapsulated; therefore, the new foaming agents should be tolerant to brines containing high quantities of divalent ions and to high temperatures.
  • Table 8 results analysis shows that the formation of supramolecular complex 12 from the 1:1:1 molecular interaction of compounds 9, 10 and 11 would be strongly favored from the thermodynamic point of view. Additionally, the -201.987 kJ/mol interaction energy indicates that ion-ion-type supramolecular interactions and/or a combination of ion-dipole interactions and hydrogen bonds would be present. Table 7. Main Mulliken atomic charges in compounds 5, 6, 7 and supramolecular complex 8.
  • Table 9 results analysis shows that the 2.414, 2.377 and 2.163 ⁇ distances for interactions O1 ⁇ Na2 , O2 ⁇ Na1 and O3 ⁇ Na1 are smaller than the Van der Waals Radius sum for the oxygen (Van der Waals Radius of 1.52 A) and sodium (Van der Waals Radius of 2.27 A) atoms and are typical of structures containing Na-O coordination bonds and sulfonate groups ( Crystal Growth & Design 2006, 6[2], 514-518 ).
  • supramolecular complex 12 shows that the sodium atoms have been encapsulated and, therefore, the new foaming agents should be tolerant to brines containing high quantities of divalent ions and to high temperatures, in addition to the fact that in order to generate nanocavities, a dimerization process of supramolecular complex 12 would be required.
  • Table 10 results show that the Mulliken atomic charge on sodium atom Na2 from supramolecular complex 12 is reduced by 0.152 units with regard to the charge that this atom has in sodium 3-hydroxy-dodecyl-1-sulfonate (sodium hydroxy alkyl sulfonate) compound 10, whereas oxygen atoms 01 and 02 atomic charges suffer a decrease of 0.092 and 0.144 units, with regard to pentyl-amido-propyl-hydroxysultaine (alkyl amido propyl hydroxysultaine) 11; this significant change in the Mulliken atomic charges confirms that in supramolecular complex 8, sodium atom Na2 is coordinated with oxygen atoms O1 and 02.
  • supramolecular complex 12 confirms the fact that in order to generate nanocavities, a dimerization process of the same supramolecular complex 12 would be required.
  • Table 10. Main Mulliken atomic charges in compounds 9, 10, 11 and in supramolecular complex 12. * Supramolecular complex molecular model Atom Atomic charge in the compound or complex (e) 9 10 11 12 O1 -0.908 -0.816 O2 -0.950 -0.806 O3 -0.879 -0.806 O4 -0.837 -0.856 O5 -0.820 -0.830 O6 -0.839 -0.880 O7 -0.845 -0.847 O8 -0.842 -0.877 O9 -0.850 -0.931 Na1 0.477 0.458 Na2 0.619 0.467 S1 2.217 2.258 S2 2.220 2.223 S3 2.227 2.258 * Hydrogen atoms were removed for better visualization.
  • Table 11 results analysis shows that the formation of supramolecular complex 16 from the 1:1:2 molecular interaction of compounds 13, 14 and 15 would be strongly favored from the thermodynamic point of view. Additionally, the -299.323 kJ/mol interaction energy indicates that ion-ion-type supramolecular interactions and/or a combination of ion-dipole interactions and hydrogen bonds would be present.
  • Table 12 results analysis shows that the 2.247, 2.235, 2.214 and 2.178 ⁇ distances for interactions O1 ⁇ Na1 , O3 ⁇ Na2 , O11 ⁇ Na1 and O12 ⁇ Na1 are smaller than the Van der Waals Radii sum for the oxygen (Van der Waals Radius of 1.52 A) and sodium (Van der Waals Radius of 2.27 A) atoms and are typical of structures containing Na-O coordination bonds and sulfonate groups ( Crystal Growth & Design 2006, 6[2], 514-518 ). Table 12. Main bond distances in compounds 13, 14, 15 and supramolecular complex 16.
  • supramolecular complex 16 reveals the presence of a nanocavity, which might act as gas receptor and generate inclusion complexes that would behave as foaming agents in aqueous media. Additionally, said complex 16 shows that the sodium atoms have been encapsulated, whereby the new foaming agents should be tolerant to brines containing large quantities of divalent ions and to high temperatures.
  • Table 13 results confirm the presence of a nanocavity in supramolecular complex 16, which might act as gas receptor and generate inclusion complexes that would behave as foaming agents in aqueous media.
  • Table 13 Mulliken atomic charges of compounds 13, 14, 15 and supramolecular complex 16.
  • Table 14 results analysis shows that the formation of supramolecular complex 20 from the 1:1:2 molecular interaction of compounds 17, 18 and 19 would be strongly favored from the thermodynamic point of view. Additionally, the -291.521kJ/mol interaction energy indicates that ion-ion-type supramolecular interactions and/or a combination of ion-dipole interactions and hydrogen bonds would be present. Table 14.
  • the geometry of the molecular complex resulting from the interaction of the compounds sodium trans -non-2-en-1-sulfonate (sodium alkenyl sulfonate) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 27 was optimized in the gas phase at 1:1:2 molecular ratios 28, as were the geometry of carbon dioxide 31 and the geometry of inclusion complex 32 generated by the interaction of complex 28 with carbon dioxide 31 (14), and the energetic results obtained for the inclusion process (15) are shown in Table 21.
  • Table 21 results shows that the formation of inclusion complex 32 by the interaction of nanocavity 28 with carbon dioxide 31 would be favored from the thermodynamic point of view. Additionally, the -4.952 kJ/mol interaction energy indicates that Van der Waals-type supramolecular interactions would be present and, therefore, supramolecular complex 28 might be used as foaming agent to control fluid channeling problems in wells where carbon dioxide is used as gas to generate foam. Table 21.
  • the geometry of the molecular complex resulting from the interaction of the compounds sodium trans -non-2-en-1-sulfonate (sodium alkenyl sulfonate) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 27 was optimized in the gas phase at 1:1:2 molecular ratios 28, as were the geometry of nitrogen 33 and the geometry of inclusion complex 34 generated by the interaction of complex 28 with nitrogen 33 (16), and the energetic results obtained for the inclusion process (17) are shown in Table 22.
  • Table 22 results shows that the formation of inclusion complex 34 from the interaction of nanocavity 28 with nitrogen 31 would be favored from the thermodynamic point of view. Additionally, the -3.827 kJ/mol interaction energy indicates that Van der Waals-type supramolecular interactions would be present and, therefore, supramolecular complex 28 might be used as foaming agent to control fluid channeling problems in wells where nitrogen is used as gas to generate foam. Table 22.
  • the geometry of the molecular complex resulting from the interaction of the compounds sodium trans -non-2-en-1-sulfonate (sodium alkenyl sulfonate) 25, sodium 3-hydroxy-hexyl-1-sulfonate 26 (sodium alkyl hydroxy sulfonate) and ethyl-amido-propyl-hydroxysultaine (alkyl amido hydroxysultaine) 27 was optimized in the gas phase at 1:1:2 molecular ratios 28, as were the geometry of n- propane 35 and the geometry of inclusion complex 36 generated by the interaction of complex 28 with n -propane 35 (18), and the energetic results obtained for the inclusion process (19) are shown in Table 23.
  • Table 23 results analysis shows that the formation of inclusion complex 36 by the interaction of nanocavity 28 with n -propane 35 would be favored from the thermodynamic point of view. Additionally, the -12.172 kJ/mol interaction energy indicates that Van der Waals-type supramolecular interactions would be present and that, therefore, supramolecular complex 28 might be used as foaming agent to control fluid channeling problems in wells where n -propane is used as gas to generate foam. Table 23.
  • This aspect is relevant in enhanced recovery processes where the use of surfactants and brines with high contents of divalent ions is intended in order to increase the recovery factor, since with supramolecular complex 37 the viscosity of the brine could be significantly increased, thereby reducing the mobility of the displacing fluid and thus generating a larger hydrocarbon volumetric sweep.
  • Table 25 results shows that the formation of supramolecular complex 40 by the interaction of two units from supramolecular complex 28 with calcium chloride 38 would be favored from the thermodynamic point of view. Additionally, the - 278.010 kJ/mol interaction energy indicates that in the calcium ions sequestration process by supramolecular complex 28, ion-dipole-type supramolecular interactions would be present and, therefore, in an aqueous medium, supramolecular complex 28 molecular weight would increase as a function of the concentration of divalent ions present in the solution. Table 25.
  • the supramolecular complexes resulting from the self-assembly process of alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines with sodium alkyl hydroxysulfonates and sodium alkenyl sulfonates have the ability to sequester divalent ions, such as calcium, and that this aspect impacts by increasing their molecular weight as a function of the concentration of divalent ions present in the solution, by means of molecular simulation, the ability of said molecular complexes to alter the wettability of carbonate rocks such as limestone and dolomite was then determined.
  • the geometry of water 49, the geometry of calcite (CaCO 3 ) surface 45 and the geometry of adsorption product 50 generated by the interaction of water 49 with calcite (CaCO 3 ) surface 45 (28) were optimized in a water-solvated medium (dielectric constant 78.54), and the energetic results obtained for the adsorption process of water 49 on calcite (CaCO 3 ) surface 45 (29) are shown in Table 28.
  • Table 28 Energetic results for the adsorption process of water 49 on calcite (CaCO 3 ) surface 45 obtained with the Density Functional Theory and the LDA-VWN functional in a water-solvated medium.
  • LDA-VWN Functional Total energy (kJ/mol) Interaction Energy (kJ/mol) 45 -295713262.347 -113.236 49 -199,362.156 50 -295,912,737.700
  • Table 29 The analysis of Table 29 results shows that guest-host complex 52 formation process is favored from the thermodynamic point of view and, therefore, it is possible that supramolecular complex 44 may be used as viscosity reducer in heavy crude oils.
  • Table 29 Energetic results obtained with the Density Functional Theory and the LDA-VWN functional in a water-solvated medium for guest-host complex 52 formation process by the interaction of supramolecular complex 44 with asphaltene dimer 51 Compound or Complex Density functional theory, LDA-VWN functional Total energy (kJ/mol) Interaction Energy (kJ/mol) 44 -1,112,3870.531 -474.783 51 -14460253.447 52 -25687110.211 Where:
  • a product to act as a corrosion inhibitor it has to form a protecting film on the metallic surface that is to be protected and that under the operating conditions present in the oil industry, the surfaces generated due to electrochemical processes and that have to be protected against corrosion consist mainly of hematite and/or pyrite ( Revista de la Sociedad Qu ⁇ mica de México 2002, 46[4], 335-340 ; Langmuir 1996, 12, 6419-6428 ).
  • the geometry of supramolecular complex resulting from the interaction of compounds sodium trans- non-2-en-1-sulfonate (sodium alkenyl sulfonate) 53, sodium 3-hydroxy-hexyl-1-sulfonate 54 (sodium alkyl hydroxysulfonate) and ethyl amido propyl hydroxysultaine (alkyl amido hydroxysultaine) 55 was optimized in a water-solvated medium (dielectric constant 78.54) at 1:1:1 molecular ratios 56, as was the geometry of hematite ( ⁇ -Fe 2 O 3 ) surface 57 and the geometry of adsorption product 58 generated by the interaction of supramolecular complex 56 with hematite ( ⁇ -Fe 2 O 3 ) surface 57 (32), and the energetic results obtained for the adsorption process of supramolecular complex 56 on hematite
  • Table 30 results shows that the adsorption process of supramolecular complex 56 on hematite ( ⁇ -Fe 2 O 3 ) surface 57 is favored from the thermodynamic point of view and, therefore, the formation of the protective film is spontaneous and supramolecular 56 might be used as corrosion inhibitor in environments that are characteristic of the oil industry.
  • the geometry of supramolecular complex resulting from the interaction of compounds sodium trans- non-2-en-1-sulfonate (sodium alkenyl sulfonate) 53, sodium 3-hydroxy-hexyl-1-sulfonate 54 (sodium alkyl hydroxy sulfonate) and ethyl-amido-propyl-hydroxysultaine (alkyl amido-hydroxysultaine) 55 was optimized in a water-solvated medium (dielectric constant 78.54) at 1:1:1 molecular ratios 56, as were the geometry of pyrite (Fe 2 S) surface 59 and the geometry of adsorption product 60 generated by the interaction of supramolecular complex 56 with pyrite (Fe 2 S) surface 59 (34), and the energetic results obtained for the adsorption process of supramolecular complex 56 on pyrite (Fe 2 S) surface
  • Table 31 results shows that the adsorption process of supramolecular complex 56 on pyrite (Fe 2 S) surface 59 is favored from the thermodynamic point of view and thus the formation of the protecting film is spontaneous and supramolecular complex 56 might be used as corrosion inhibitor in environments that are characteristic of the oil industry.
  • a comparison of the adsorption results obtained by means of molecular simulation for supramolecular complex 56 on hematite ( ⁇ -Fe 2 O 3 ) 57 and pyrite (Fe 2 S) 59 surfaces indicates that the protecting film that supramolecular complex 56 would form on the hematite ( ⁇ -Fe 2 O 3 ) surface would be more stable than the film that it would form on pyrite (Fe 2 S) surface 59 and that in both types of surfaces, supramolecular complex 56 might be used as corrosion inhibitor.
  • the supramolecular complexes derived from the present invention are obtained according to the synthesis procedure (36) that consists in mixing sodium alkyl hydroxysulfonates, sodium alkenyl sulfonates with alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines at room temperature and atmospheric pressure.
  • the molar ratio at which supramolecular complexes are formed is within the ranges of 1:1:7 to 7:7:1, respectively, with molar ratios within the range of 1:1:2 to 1:2:4 being preferred.
  • supramolecular complexes from sodium alkyl hydroxysulfonates, sodium alkenyl sulfonates with alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines can be carried out in water, brines, alcohols or a water-alcohols mixture, with the aqueous medium being preferred.
  • the final concentration by weight of the supramolecular complexes in the mixture may vary from 0.1% to 50%, preferably within the range of 20% to 50%.
  • Sodium alkenyl sulfonates useful for the present invention include sodium but-2-en-1-sulfonate, sodium pent-2-en-1-sulfonate, sodium hex-2-en-1-sulfonate, sodium hept-2-en-1-sulfonate, sodium oct-2-en-1-sulfonate, sodium non-2-en-1-sulfonate, sodium dec-2-en-1-sulfonate, sodium undec-2-en-1-sulfonate, sodium dodec-2-en-1-sulfonate, sodium tetradec-2-en-1-sulfonate, sodium hexadec-2-en-1-sulfonate and the mixture of two or more of these sodium alkenyl-sulfonates.
  • Sodium alkyl hydroxysulfonates useful for the present invention include sodium 3-hydroxybutane-1-sulfonate, sodium 3-hydroxypentane-1-sulfonate, sodium 3-hydroxyhexane-1-sulfonate, sodium 3-hydroxyheptane-1-sulfonate, sodium 3-hydroxyoctane-1-sulfonate, sodium 3-hydroxynonane-1-sulfonate, sodium 3-hydroxydecane-1-sulfonate, sodium 3-hydroxyundecane-1-sulfonate, sodium 3-hydroxydodecane-1-sulfonate, sodium 3-hydroxytetradecane-1-sulfonate, sodium 3-hydroxyhexadecane-1-suffonate, sodium 2-hydroxybutane-1-sulfonate, sodium 2-hydroxypentane-1-sulfonate, sodium 2-hydroxyhexane-1-sulfonate, sodium 2-hydroxyheptane-1-sulfonate, sodium 2-hydroxyoctane-1-
  • Alkyl amido propyl hydroxysultaines useful for the present invention include ethyl-amido-propyl-hydroxysultaine, propyl-amido-propyl-hydroxysultaine, butyl-amido-propyl-hydroxysultaine, pentyl-amido-propyl-hydroxysultaine, hexyl-amido-propyl-hydroxysultaine, heptyl-amido-propyl-hydroxysultaine, octyl-amido-propil-hydroxisultaine, nonyl-amido-propyl-hydroxysultaine, decyl-amido-propyl-hydroxysultaine, undecyl-amido-propyl-hydroxysultaine, dodecyl-amido-propyl-hydroxysultaine, tetradecyl-amido-propyl-hydroxysultaine, hexadecyl-amido
  • Alkyl hydroxysultaines useful for the present invention include ethyl-hydroxysultaine, propyl-hydroxysultaine, butyl-hydroxysultaine, pentyl-hydroxysultaine, hexyl-hydroxysultaine, heptyl-hydroxysultaine, octyl-hydroxysultaine, nonyl-hydroxysultaine, decyl-hydroxysultaine, undecyl-hydroxysultaine, dodecyl-hydroxysultaine, tetradecyl-hydroxysultaine, hexadecyl-hydroxysultaine, coco-hydroxysultaine and mixtures of two or more of these alkyl hydroxysultaines.
  • the infrared (IR) spectrum of example 19 supramolecular complexes was obtained by means of ATR and it shows the following main vibration bands: 1) A symmetric, intense, wide tension band at 1648 cm -1 assigned to the vibration of the amide carbonyl group, 2) An asymmetric, intense, wide tension band at 1550 cm -1 assigned to the amide carbonyl group vibration, 3) An asymmetric, intense, wide tension band at 1175 cm -1 assigned to the sulfonate group vibration and 4) A symmetric middle-intensity tension band at 1037 cm -1 assigned to sulfonate group vibration.
  • the following characteristic signals are onserved: 1) A symmetric, intense, wide tension band at 1641 cm -1 assigned to the amide carbonyl group vibration, 2) An asymmetric, intense, wide tension band at 1549 cm -1 assigned to the amide carbonyl group vibration, 3) An asymmetric, intense, wide tension band at 1189 cm -1 assigned to the sulfonate group vibration and 4) A symmetric, middle-intensity tension band at 1039 cm -1 assigned to the sulfonate group vibration.
  • Figures No. 1, 2, 3 and 4 show the typical NMR 1 H and 13 C spectra of the coco-amido-propyl hydroxysultaine and the sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate-mixture raw materials, respectively
  • Figures No. 5 and 6 show the NMR 1 H y 13 C spectra of supramolecular complexes (36) described in Example 19
  • figures 7 and 8 show the Infrared spectra of coco-amido-propyl hydroxysultaine and supramolecular complexes (36) described in Example 19, respectively.
  • the measurement is based on applying the nephelometric technique by using a photometer.
  • the standard method is based on the comparison of the amount of light dispersed by the colloidal particles present in a sample of water with the intensity of the light emerging across the same sample.
  • Table 32 shows the compositions of the brines that were used in the fase stability assessment of the supramolecular complexes described in Examples 19, 20 and 21 and Table 33 shows the results obtained at the corresponding evaluation at room temperature. It is worth mentioning that in order to pass this test, a value 30 NTU should not be exceeded.
  • Table 33 indicates that supramolecular complexes described in Examples 19, 20 and 21 are soluble and tolerant to levels of salinity and hardness ranging from 32803 to 253859 ppm and from 6420 to 87700 ppm, respectively.
  • phase stability comparative tests were conducted with regard to the raw materials used for the synthesis thereof and with the supramolecular complexes described in the Mexican patent MX 297297 . The results are shown in Table 34.
  • Table 34 analysis indicates that the mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate and supramolecular complexes from Mexican patent MX 297297 show phase stability problems at salinities from 253859 ppm on and levels of hardness from 87700 ppm on (see Table 32). Additionally, a comparison of Tables No. 33 and 34 results demonstrates the advantage of using the supramolecular complexes (36) object of the present invention in brines with ultra-high salinities and high levels of hardness.
  • viscosifying agents of the poly-(sodium acrylamide- co -2-acrylamido-2-methyl-1-propanesulfonate)-type viscosifying agents such as terpolymers based on acrylamide/N-vinyl pyrrolidone/2-acrylamido-2-methy-1-propane sodium sulfonate and foam stabilizers based on itaconic acid- and sodium vinyl sulfonate- derived copolymers
  • Hernández-Altamirano, Ra ⁇ l; Tesis de Doctorado 2010; Desarrollo de productos quimicos multifuncionales con vasios
  • Table 36 analysis indicates that the addition to supramolecular complexes (36) of the corrossion inhibitors based on zwitterionic geminal liquids described in the US patent application 2011/0138683 A1 , viscosifying agents of the poly-(sodium acrylamide- co -2-acrylamido-2-methyl-1-propane sulfonate)-type, viscosifying agents such as terpolimers based on acrylamide/N-vinyl pyrrolidone/2-acrylamido-2-methy-1-propane sodium sulfonate and foam stabilizers based on itaconic acid- and sodium vinyl sulfonate-derived copolymers does not generate any phase stability problem.
  • the assessment of the foaming capability of the supramolecular complexes resulting from the interaction of sodium alkyl hydroxysulfonates, sodium alkenyl sulfonates and alkyl amido propyl hydroxysultaines or alkyl hydroxysultaines object of the present invention (36) was performed using two different tests: a) Measurement of foam stability at atmospheric conditions (Foaming test at atmospheric pressure), b) Measurement of foam stability at high pressure, high temperature and ultra-high salinity conditions (Foaming test at high pressure) and c) Determination of rheological properties.
  • the foaming system consists of three sub-systems, with the first one being the body of the foam meter, which comprises two concentric glass tubes.
  • the external tube measures 1.35 m high with a diameter of 0.0762 m, and the inner tube is 1.15 m high, with a diameter of 0.0508 m.
  • the solution to be evaluated (brine plus chemical product) is charged in the inner tube and the generation and confinement of the foam is carried out, whereas the function of the external tube is to hold the heating fluid whereby the temperature of the test is controlled.
  • the second sub-system is the one that controls the flow of gas and comprises a storage tank whereby the gas discharge pressure is regulated and a second stabilization tank of smaller dimensions is intended to contribute to the regulation of the flow of gas and prevent condensate entrainment.
  • the gas line has a three-valve set intended to control the direction and magnitude of the flow of gas: the first is a venting valve connected to the stabilization tank; next, there is a flow valve, which allows for the gas to be fed into a calibrated flow-meter (maximum flow, 100 cm 3 /min), and finally, there is a three-way valve intended to control the admittance of gas to the foam meter body, as well as to open the system to the atmosphere.
  • this sub-system there is a stainless steel tubing section or spear with a diffuser or disperser (which can be made out of glass or steel) coupled to its lower end, through which the gas is injected to the liquid phase in order to distribute the flow of gas homogeneously and to achieve a monodisperse foam texture.
  • a diffuser or disperser which can be made out of glass or steel
  • the third sub-system is the one that controls the temperature in the ringshaped space by means of the flow of heating oil controlled by a digital recirculation thermal bath.
  • Foam stability is defined as the variation of the initial height of the foam with regard to time and it is determined according to equations 1 and 2.
  • H l - H l H e
  • H eMAX is the H e calculated at 45 seconds of the experiment.
  • Table 37 The composition of the brine used to dilute the supramolecular complex is shown in Table 37.
  • Table 37 BRINE 1 CATIONS mg/L SODIUM 11742.1 CALCIUM 448 MAGNESIUM 1288.4 ANIONS mg/L CHLORIDES 19900 SULFATES 3650 CARBONATES 13.2 BICARBONATES 84.2 TOTAL HARDNESS AS CaCO 3 6420 SALINITY AS NaCl 32803.9
  • Figure 10 shows the time versus stability graph of the foam obtained with supramolecular complexes described in Examples 19, 20 y 21 and whose basic structural formula is indicated in (36), which reveals that the minimum stability of 30% is reached in a time of 385, 360 and 345 minutes, respectively.
  • the foam generated by supramolecular complexes described in examples 19, 20 and 21 and whose basic structural formula is indicated in (36), is at least 10-fold more stable than the foams generated by the mixture of sodium 3-hydroxydodecane-1-sulfonate and sodium dodec-2-en-1-sulfonate, 7-fold more stable than those generated by coco amido propyl hydroxysultaine and 2-fold more stable than those generated by the coco amido propyl betaine-, sodium alpha olefin sulfonate- and dodecyl trimethyl ammonium chloride- derived supramolecular complex.
  • the stability of the foam generated by the supramolecular complex described in example 19 is 17% more stable than that generated by the coco amido propyl betaine-, sodium alpha olefin sulfonate-, dodecyl trimethyl ammonium chloride- and poly(itaconic acid)-derived complex.
  • Figure 12 shows the time versus stability graph of the foam obtained with formulations 1, 2, 3 and 4, which reveals that the minimum stability of 30% is reached in a time of 240, 250, 375 and 440 minutes, respectively.
  • the stability assessment of the foam generated by supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36) was carried out by means of the foaming test at atmospheric pressure, at a temperature of 70 °C, using a brine containing 313203 ppm of salinity as NaCl, out of which 154000 ppm corresponded to divalent ions (Calcium and Magnesium), a concentration of supramolecular complex of 0.2% by weight, and methane (CH 4 ), carbon dioxide (CO 2 ) and nitrogen (N 2 ) as gases.
  • Foaming test at high pressure The foam generation system at high pressure and high temperature that was used was developed at the hydrocarbon recovery laboratory of the Instituto Mexicano del Petróleo and it is designed to assess the stability of surfactant-generated foams at temperatures up to 170°C and pressures as high as 6000 psi and it is shown in Figure 15 . It comprises injection pumps, transfer cylinders, inverse pressure regulator (IPR), temperature control system, pressure monitoring system, digital camera, filter (foam generator) and experimental cell.
  • IPR inverse pressure regulator
  • Figure 16 shows the photographic images sequence of the foam formed by brine plus supramolecular complex at a concentration of 0.2% by weight, by means of which the behavior of the foam is observed during the test. Its duration was about 168 h, time during which the conditions of the system were maintained constant at a temperature of 150 °C and 3500 psi of pressure.
  • Table 39 The results of the test are shown in Table 39 and indicate that the foam is stable under high pressure, ultra-high salinity and high temperature conditions and it did not get to coalesce completely during the 168 h.
  • Table 39 % Area of lamellae Time (h) % Area of lamellae Time (h) 100 0 55 73.5 90 12 55 73.9 80 24 52 89 75 36 50 94 68 65 44 98 68 66 44 116 68 67 44 118 65 68 40 122 65 69 38 137 65 69.2 33 144 60 70.2 31 146 60 70.8 28 161 55 72.3 27 164
  • Figure 17 shows the behavior of time against foam stability under formation conditions.
  • the testing method consists in determining the rheological behavior of foams generated by the supramolecular complexes object of the present invention, with ultra-high salinity and high hardness water under reservoir conditions using a capillary rheometer for high pressures and high temperatures by means of an experimental method developed at the well productivity laboratory of the Instituto Mexicano del Petróleo, which determines the pressure drop between two points of the capillary tube as a function of the flow of foam.
  • viscosity can be calculated as a function of the shear rate, and the results are shown in Table 42.
  • Experimental Apparent Viscosity (cP) Calculated Apparent Viscosity (cP) 1175.30 11.32 11.51 1007.41 12.36 12.63 839.51 13.85 14.10 671.61 16.51 16.12 587.66 18.49 17.47 503.69 20.12 19.18 419.75 21.02 21.40 335.81 23.31 24.48 251.85 27.14 29.11 167.92 38.98 37.16
  • Example 19 The determination of the rheologic behavior of a foam generated by supramolecular complex described in Example 19 and whose basic structural formula is indicated in (36) was carried out at a temperature of 150°C and a pressure of 3500 psi at a concentration of 0.2% by weight in brine 4 whose composition is described in Example 27, employing as gas nitrogen in order to reach a quality of 80% and within a range of low shear rates.
  • Table 43 summarizes the most relevant conditions of the experiment and the capillary dimensions.
  • Table 44 below and Figure 19 show the results obtained.
  • viscosity can be calculated as a function of shear rate and the results are shown in Table 45.
  • Table 45 Shear rate (1/s)
  • Experimental Apparent Viscosity (cP) Calculated Apparent Viscosity (cP) 305.71 6.00 5.95 254.76 7.00 6.82 203.81 8.00 8.06 152.85 11.00 9.99 101.90 15.00 13.53 76.43 17.00 16.78 67.94 18.00 18.32 59.44 18.70 20.24 33.97 29.00 30.75 25.48 35.00 38.13 16.98 50.00 51.62 12.74 65.00 64.01
  • the testing method comprises a procedure to observe how the contact angle of a rock/oil system immersed in brine with high contents of total solids dissolved and divalent ions such as calcium and magnesium with or without the presence of chemical product is modified at environmental conditions in order to determine the time that it takes for small proportions of oil to detach in the system.
  • Tables 47, 48 and 49 show the results of the contact angle change experiment using the supramolecular complex described in Example 19 at different concentrations.
  • supramolecular complex described in example 19 favorably modifies the contact angle and detaches the oil in less than 1 hour of having contact with the oil adsorbed on the rock under environmental conditions and using high-salinity brines, as well as oils with high contents of asphaltenes.
  • the testing method consists in determining the oil recovery factor at different temperatures, due to spontaneous water imbibition processes in small fragments of carbonate rock and/or nuclei with known permeabilities and porosities.
  • Table 51 shows the cumulative results of the recovery factor along the range of temperatures.
  • PRODUCT IMBIBED OIL gr
  • RECOVERED OIL gr
  • CUMULATIVE RECOVERY FACTOR %
  • Table 53 shows the result of the cumulative recovery factor within the range of temperatures for supramolecular complexes described in Examples 19 and 20.
  • Table 53 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) CUMULATIVE RECOVERY FACTOR (%) BRINE 1 1.544 0.080 5.2 Supramolecular complex described in Example 19 1.479 0.144 9.7 Supramolecular complex described in Example 20 1.511 0.129 8.6
  • Figure 23 shows the Amott cell containing the supramolecular derived from Example 19.
  • Table 54 shows the result of the cumulative recovery factor within the temperature interval for formulation 3 whose composition is described in Example 23.
  • Table 54 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) CUMULATIVE RECOVERY FACTOR (%) BRINE 1 1.544 0.080 5.2 Formulation 3 1.900 0.299 15.7
  • the testing method consists in determining the oil recovery factor at different temperatures, due to spontaneous water imbibition processes in small nuclei of carbonate rock with known permeabilities and porosities.
  • Tables 55 and 56 show the characteristics of the oil and the limestone cores used. Table 55 Nucleus dimensions (cm) Absolute permeability to helium (mD) Nucleus porosity (%) 3.8 x 7 115 20 Table 56 Fraction Saturated (% weight) 40.91 Aromatics (% weight) 36.13 Resins (% weight) 22.30 Asphaltenes (% weight) 0.20
  • Table 57 shows the result of total recovery factor for supramolecular complex described in example 19 at a concentration of 0.2% by weight.
  • Table 57 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) CUMULATIVE RECOVERY FACTOR (%) BRINE 4 10.0323 0.5911 5.9 Supramolecular complex described in Example 19 10.2047 1.6990 16.7
  • Figure 24 shows the saturated core and the detachment of oil.
  • the equipment comprises a glass-lined reactor where a nucleus, previously soaked with oil, is introduced and gets in contact with an aqueous medium with chemical product.
  • the experimental conditions are the following:
  • FIG. 25 shows the equipment used.
  • Table 59 shows the result of the recovery factor at a temperature of 150°C and pressure of 140 psi for supramolecular complex described in Example 19.
  • Table 59 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) RECOVERY FACTOR (%) BRINE 4 10.7448 1.2 11.2 Supramolecular complex described in Example 19 10.2046 3.25 31.9
  • Figures 26 and 27 show the rock core used inside the reactor, as well as the detachment of oil due to the effect of the supramolecular complex, respectively.
  • Table 61 shows the recovery factor result at a temperature of 150°C and a pressure of 140 psi for supramolecular complex described in Example 19.
  • Table 61 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) RECOVERY FACTOR (%) BRINE 4 57.1 7.81 13.7 Supramolecular complex described in Example 19 63.0 17.39 27.6
  • Figure 28 shows the rock nucleus used inside the reactor and figure 29 shows the detachment of crude oil due to the effect of supramolecular complex described in Example 19.
  • Table 63 shows the results of the recovery factor at a temperature of 150°C and a pressure of 140 psi for formulation 3.
  • Table 63 PRODUCT IMBIBED OIL (g) RECOVERED OIL (g) RECOVERY FACTOR(%) BRINE 4 57.1 7.81 13.7 Formulation 3 52.4 15.85 30.3
  • the methodology consists in the quantitative determination of adsorption my means of high performance liquid chromatography of a chemical product in contact with carbonate-type mineral.
  • Example 19 The determination of adsorption of supramolecular complex described in Example 19 was carried out on limestone at a concentration of 0.2 % by weight (2000 ppm) using brine 4, whose characteristics are presented in Example 27.
  • the adsorption result for supramolecular complex derived from example 19 for a concentration of 2000 ppm was 5.0 mg of supramolecular complex/g of rock.
  • Table 64 shows the viscosity and shear rate results at two different temperatures.
  • Shear rate (1/s) Viscosity (cps) at 25°C Viscosity (cps) at 40°C Non-additivated oil Oil additivated with Example 19 supramolecular complex
  • Non-additivated oil Oil additivated with Example 19 supramolecular complex 1.00 1236.24 330.77 979.24 316.40 2.16 1229.75 329.19 981.98 316.30 3.33 1222.97 325.74 982.08 313.64 4.10 1218.17 324.55 982.24 312.95 5.27 1211.14 323.61 980.11 312.35 6.04 1207.13 323.07 980.50 312.19 7.20 1200.16 322.15 979.45 311.57 8.37 1193.50 321.66 978.66 311.47 9.14 1190.68 320.87 978.10 310.79 10.30 1184.91 320.33
  • Example 19 supramolecular complex reduces the viscosity of crude oil by approximately 20 and 4% at 25 and 40°C, respectively.
  • Figures 30 and 31 show the shear rate versus viscosity graphs for non-additivated oil and for oil additivated with example 19 supramolecular complex at 25 and 40°C.
  • Example 19 The assessment of the efficiency as corrosion inhibitor was carried out for supramolecular complex described in Example 19 at a concentration of 0.2% by weight (2000 ppm), using as test medium brine 4 and crude oil whose compositions are described in Examples 27 and 35, respectively.
  • Table 65 Temperature 70°C Aqueous Medium Brine with 600+/- 50 ppm of H 2 S Duration of the test 46 hours Organic medium Crude oil Brine/Organic medium ratio by weight 90/10 Volume of the test 180mL Medium pH 4.8 Corrosion witness (metal coupons) SAE 1010 Steel
  • compositions of the brine and the crude oil are described in Examples 27 and 35.
  • the weight difference of the coupons before and after having been exposed to the corrosive medium for 46 hours is a direct indication of the metal lost due to corrosion.
  • Table 66 shows the results for supramolecular complex 37 and formulation 40, at a concentration of 2000 ppm.
  • Figure 32 shows the metal coupons used in the test.
  • Table 66 Product Corrosion rate (mpy) Efficiency (%) Reference 35.0 -- Supramolecular comples described in Example 19 4.3 87.7 *mpy: milli-inches per year
  • Example 19 of the present invention has anti-corrosive properties in acidic environments and with high salinity, characteristic of crude oil production pipelines.
  • Table 67 shows the results of corrosion inhibition efficiency for formulation 3.
  • Table 67 Product Corrosion rate (mpy) Efficiency (%) Reference 35.0 -- Formulation 3 3.2 91.0 *mpy: milli-inches per year
  • Determination of acute toxicity The determination of acute toxicity was carried out using two methods widely used throughout the world to measure the level of a pure substance or mixtures: I) Determination of acute toxicity by means of the Microtox® method and II) Assessment of acute toxicity with Daphnia Magna.
  • the Microtox® bacterial bio-assay designed by Strategic Diagnostic Inc. (Azur Environmental) is based on monitoring changes in the emissions of natural light by a luminescent bacteria, Vibrio fischeri ( Photobacterium phosphoreum ) .
  • the Microtox assay measures the acute toxicity of the test substance present in aqueous solution that uses a suspension of approximately one million of luminescent bacteria ( Photobacterium Phosphoreum ) as test organism.
  • the suspension of micro-organisms is added to a series of tubes of dilutions at controlled temperature with different concentrations of the test substance, to subsequently read, in a photometric device, the intensity of light emitted by each dilution, considering a reference blank where the test substance is not present.
  • the CE 50 is a measure of the decrease in the light emitted by the bioluminescent bacteria by means of the analyzing equipment, and specifically represents the concentration at which a 50 percent decrease of the light was obtained, with regard to a reference blank. Concretely, the CE 50 value indicates the relative toxicity of the test substance.
  • Table 68 shows the average toxicity results of a total of three repetitions.
  • This method is applicable to acute toxicity assessment in water and water-soluble substances.
  • the Daphnia gender species are the most widely used as bio-indicators in toxicity tests, due to their wide geographic distribution, the important role they play within the zooplankton community, and because they are easy to culture in laboratory and they are responsive to a wide range of toxics.
  • Table 69 shows the average toxicity results of a total of three repetitions, out of which a standard deviation of 0.15 and a variation coefficient of 1.92% were obtained.
  • Table 69 Chemical product CE 50 (ppm) *Toxicity category Supramolecular complex derived from example 19 8.18 Moderately toxic 8.10 Moderately toxic 7.82 Moderately toxic Average 8.03 Moderately toxic * Concentration range in ppm, classification a , category 5: 0.01-0.10, extremely toxic; 4: 0.1-1.0, highly toxic; 3: 1-10, moderately toxic; 2: 10-100, slightly toxic; 1: 100-1000, particularly non-toxic and 0: > 1000, non-toxic.
  • a CNS (UK) toxicity category for the application of chemical products used in hydrocarbon production in the North Sea.
  • Example 19 The acute toxicity results indicate that supramolecular complex derived from Example 19 is moderately toxic to the freshwater organism daphnia magna.
EP13187430.7A 2012-12-05 2013-10-04 Schäumzusammensetzung mit benetzbarkeitsmodifizierenden und korrosionshemmenden eigenschaften für hohe temperaturen und ultrahohen salzgehalt Active EP2740781B1 (de)

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EP3023476A1 (de) * 2014-11-18 2016-05-25 Instituto Mexicano Del Petróleo Multifunktionelle schäumungszusammensetzung mit benetzbarkeitsmodifizierungs-, korrosionhemmungs- und wassersteinhemmungs-/-dispergenseigenschaften für hohe temperaturen und ultrahohen salzgehalt
EP3031796A1 (de) * 2014-12-11 2016-06-15 Instituto Mexicano Del Petróleo Hydroxypropylbetainbasierte, zwitterionische geminale flüssigkeiten, herstellungsverfahren und verwendung als benetzbarkeitsmodifikatoren mit hemmungs-/dispergenseigenschaften von asphaltenen

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US9469804B2 (en) 2016-10-18
US20140151041A1 (en) 2014-06-05
BR102013024720B1 (pt) 2021-05-25
CA2828519C (en) 2016-10-18
CN103849366A (zh) 2014-06-11
MX2012014187A (es) 2014-06-24
EP2740781B1 (de) 2015-12-30
PH12013000298B1 (en) 2015-04-20
MX338862B (es) 2016-04-28
CA2828519A1 (en) 2014-06-05
PH12013000298A1 (en) 2015-04-20
CO7240101A1 (es) 2015-04-17

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